Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and alumina
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

• This invention relates to an improved process for the catalytic hydrogenation of the distillation residuum-containing petroleum hydrocarbons and to an improved catalyst for use therein, whereby the difliculties encountered heretofore in carrying out the process stably and with good activity over a prolonged period of time have been overcome.
• the invention relates to a process for the treatment of petroleum hydrocarbons which comprises the hydrogenation of the distillation residuum-containing petroleum hydrocarbons in the presence of a catalyst which has been obtained in the following manner.
• a dispersion mixture consisting of a sol selected from the group consisting of a hydrosol of basic aluminum sulfate and a hydrosol mixture of said hydrosol with a hydrosol of silica and containing dispersed therein -65 by weight, based on the carrier material to be obtained, of particles selected from the group consisting of water-insoluble inorganic solids and hydrogels thereof is passed through an waterimmiscible inert liquid medium to form a spherical gelled product, which is water-washed and desulfated, followed by drying and calcination to yield the carrier material which by being impregnated with an aqueous solution of a hydrogenatively active metal compound and thereafter calcinated at a temperature above 350 C. provides the catalyst for use in the afores
• the carrier material utilized is one prepared by using a dispersion mixture from which either the aforesaid particles selected from the group consisting of the waterinsoluble inorganic solids and hydrogels thereof have been omitted or have been incorporated in an amount less than 5%, say, only 4% and also, as illustrated similarly by means of the hereinafter given control experiments, that the ends of the present invention likewise cannot be achieved when the calcination temperature used in accomplishing the support of the known hydrogenatively active metal on the carrier is less than 350 C., for example, when the temperature falls to 300 C.
• an object of the present invention is to provide an improved process and an improved catalyst composition therefor by which the heretofore difficult catalytic hydrogenation treatment of the distillation residuum-containing petroleum hydrocarbons can be continuously carried out while maintaining the good activity of the catalyst stably over a prolonged period of time.
• the catalyst used in the present invention is obtained in the following manner. Particles selected from the group consisting of water-insoluble inorganic solids and hydrogels thereof are uniformly dispersed in either a hydrosol of basic aluminum sulfate (hereinafter referred to at times as alumina type hydrosol) or a hydrosol mixture of this hydrosol with a hydrosol of silica (hereinafter referred to at times as a silica-alumina type hydrosol), in an amount within a specific range.
• a hydrosol of basic aluminum sulfate hereinafter referred to at times as alumina type hydrosol
• silica-alumina type hydrosol hydrosol of silica
• the so obtained gel is then removed of its sulfate radicals by contacting the gel with an aqueous alkaline solution, followed by drying and calcining the gel, and preferably calcining it at, say, above 750 C. after drying it to obtain a spherical alumina or silica-alumina carrier material, which is immersed in an aqueous solution of a hydrogenatively active metal compound and thereafter usually dried and calcined at above 350 C. to obtain the intended catalyst.
• the alumina type hydrosol is obtained commercially as a supernatant liquid by adding powdered calcium carbonate slowly to concentrated aqueous aluminum sulfate with vigorous stirring to precipitate the sulfate radicals as calcium sulfate.
• the molar ratio of SO /Al O in this hydrosol is suitably in the range of 0.8-1.6.
• Such ions as Na", K'', Mg, Ca++, Zn++, Fe++ and NH may be present as impurities in the aqueous aluminum sulfate used in the present invention as the starting material.
• the silica-aluminum type hydrosol is obtained by merely mixing an alumina type hydrosol with a hydrosol of silica.
• a water-insoluble inorganic solid or a hydrosol thereof is dispersed finely in the fore going alumina type or silica-alumina type hydrosol.
• any inorganic solid can be used without any particular restrictions so long as it is one which does not substantially dissolve in water as well as does not decompose in the aforesaid hydrosol nor otherwise sets up a chemical change.
• the hydrogels of these inorganic solids can also be fully used for the purpose of invention. A number of examples of such a substance will be given below.
• Silica gel silica hydrogel and powdered quartz.
• Silica-alumina type substances silica hydrogel and powdered quartz.
• Silica-alumina type gel silica-alumina type hydrogel, acid clay, activated clay, kaolinite, montmorillonite, bentonite and other like clayey minerals and aluminosilicates, e.g. natural or synthetic zeolite.
• oxides, hydroxides or sulfides of such metals as iron, cobalt, nickel, molybdenum and copper.
• the foregoing inorganic solids one which is porous, for example, one whose specific surface area is greater than 50 square meters per gram, be used. It is also, of course, possible to use the foregoing metal oxides, hydroxides or sulfides having catalytic activity, though their specific surface area itself may be small. These solid materials need not necessarily be used singly but may also be used in combination of two or more classes.
• these inorganic solids or hydrogels thereof are added to the alumina type or silicaalumina type hydrosol in such a proportion that the content therein becomes to 65% by weight, and preferably -50% by weight, based on the resulting carrier material.
• the inorganic solids are added in an amount such that the proportion is less than 5% by Weight, the desired effects are not noted and the ends of the invention cannot be attained.
• this addition is in such a proportion that 65% by weight is exceeded, either the formation of the spherical gelled product becomes difficult or the particles of the spherical gelled product, even though capable of being formed, suffers such a reduction in strength as to be not serviceable.
• the particles selected from the aforesaid inorganic solids or the hydrogels thereof be commingled in the alumina type or silica-alumina type hydrosol in as finely divided state as possible for imparting the desired activity without a substantial decline in the particle strength of the spherical gelled product formed.
• the inorganic solids have a particle diamter of less than 74 microns (ZOO-mesh size), and especially less than 30 microns.
• the hydrogel of an inorganic solid when the hydrogel of an inorganic solid is to be used, it is preferred that the hydrogel be finely dispersed in the alumina type or silica-alumina type hydrosol by mixing in a conventional rotating ball mill on the order of about 10 minutes.
• a homogeneous mixture wherein either an inorganic solid material or a hydrogel thereof is dispersed uniformly in a finely divided state in either an alumina type or silica-alumina type hydrosol is obtained.
• This dispersion mixture is then passed through a water-immiscible inert liquid medium to form the spherical gelled product of the invention.
• an organic medium which is water-immiscible and inert to the aforesaid dispersion mixture is used, preferably useable being the petroleum hydrocarbons.
• the temperature of the liquid medium is suitably varied depending upon the time required for passing the dispersion mixture therethrough and effecting the gelation and the size desired for the spherical gelled product, but usually a liquid warmed or heated at 40-100 C. is used.
• this time is suitably varied depending upon the temperature of the liquid medium and the siZe desired for the spherical gelled product.
• the spherical gelled product used in the present invention need not be a perfect sphere but will sufiice if nearly so. Hence, it is to be understood that the spherical gelled product, as referred to herein, is not a term denoting a perfect sphere.
• the size of the hydrogel and hence the size of the carrier material, can be regulated over a broad range as a result of its relationship with the size of the nozzle from which the dispersion mixture is discharged into the heated liquid medium, the difference in specific gravities of the dispersion mixture and the medium, and the viscosity and surface tension of the dispersion mixture.
• the addition of preferably 10-30% by weight of water is made to the dispersion mixture prior to its being passed through and heated in the liquid medium, the addition being preferably made as immediately prior to this operation as possible.
• the gas contained dissolved in the dispersion mixture is preferably eliminated prior to the operation.
• the spherical hydrogel formed is subjected to hydrolysis by pouring fresh water or hot water thereon to remove a part of the sulfate radicals, thus rendering it stable and preventing its reversion to a sol. Next, it is brought into contact with an aqueous alkaline solution to gradually raise its pH, thereby eliminating the remaining sulfate radicals as sulfates.
• aqueous caustic alkali solutions and aqueous alkali carbonate solutions can be used as the foregoing aqueous alkaline solution
• aqueous alkaline solutions such as ammonia water and aqueous urea solution can be recommended.
• An abrupt raising of the pH is not desirable, since cracks will form in the hydrogel which, upon drying, will result in breakage of the hydrogel or reduction in its pressure resisting strength or resistance to attrition and hence make it easily breakable.
• the sulfate radicals are removed as completely as possible by washmg with water, after which the spherical hydrogel product is dried and calcined.
• the drying operation is preferably carried out slowly in the presence of saturated steam, since cracks will form in the hydrogel if the drying is carried out too hastily.
• the spherical hydrogel is dried and then also calcined. Since a tendency to a decline in the desulfurization activity takes place if the calcination temperature is too high, it is preferred in this invention to carry out the calcination at a temperature ranging, say, from 350 to 750 C. A calcination time of 1-3 hours is preferred.
• the spherical carrier material obtained as hereinabove described has great pressure resisting strength and heat resistance and does not easily crack. This is used for preparing the catalyst to be used in the invention process.
• the so obtained carrier material is then immersed in an aqueous solution of a hydrogenatively active metal compound, followed by drying and calcination to obtain the intended catalyst.
• the hydrogenatively active metals suitably used are the various metals which are useable as hydrogenation treatment catalysts, such, for example, as one or more metals selected from he m tals of G o ps VI and VIII of the periodic table, particularly cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten.
• the water-soluble compounds of such metals include such, for example, as the nitrates and ammonium salts of these metals.
• the calcination temperature used in preparing the catalyst is too low, an effective activity is not demonstrated. Hence, the calcination must be conducted at a temperature above 350 C. Usually, a temperature range on the order of 350-600 C. is employed.
• the invention process can be carried out either continuously or batchwise. Further, in carrying out the process continuously, the various known methods such as the fixed, moving or fluidized bed technique can be employed.
• the catalyst may be used in its as-obtained state, its presulfiding may also be carried out.
• the presulfiding of the catalyst can be carried out in customary manner.
• the invention process is particularly preferred for carrying out the hydrodesulfurization of the distillation residuum-containing petroleum hydrocarbons.
• the silica content of the carrier material should preferably be reduced.
• the addition of the silica component in preparing the carrier material is made such that its content therein becomes not greater than a SiO /(Al O+SiO weight ratio of 0.3.
• reaction conditions in carrying out the hydrodesulfurization of the distillation residuum-containing petroleum hydrocarbons usually range as follows: temperature 300-500 0., pressure 50-300 kg./cm. g., liquid hourly space velocity of the feedstock oil 0.2- vol./vo1./ hr., and flow rate ratio of hydrogen to feedstock oil 300- 3000 liter-NTP/ liter; an optimum combination of the various conditions being chosen in accordance with the properties of the feedstock oil and the properties required in the resulting product.
• the desulfured oil leaving the reaction column is submitted to steam stripping, reduced pressure steam stripping, vacuum or atmospheric distillation, or a combination of these treatments to obtain the final product.
• the hydrosol of silica was added as the water-insoluble inorganic solid material finely divided aluminum hydroxide (boehmite) comminuted to less than 10 microns in the amounts of respectively 0.5, 4, 8, 15 and 22 grams.
• Each of the mixed specimens was placed in a 7-liter ball mill and the three components were uniformly dispersed by agitation for 20 minutes. The dispersion mixture was then allowed to drop from the top of a granulation column filled with a solvent mixture of spindle oil and trichlorobenzene (sp. gr. 1.210/ 15 C.). The solvent was maintained at 85 C. with a heater. The sol was heated in the solvent and became a spherical hydrogel of 2-4 mm.
• the hydrogel at the bottom of the column was withdrawn via a pipe and introduced to a separately provided tank filled with water.
• the operation of adding hot water to the tank containing the hydrogel and discarding the hot water was repeated from 5 to 8 times, using fresh water each time.
• a part of the about 1.12 mols of sulfate radicals bonded to the hydrogel was washed out by hydrolytic action to reduce the sulfate radicals bonded to about 0.63 on the basis of molar ratio SO /Al O of the hydrogel.
• a single spherical carrier is clasped between a pair of steel plates disposed in parallel and pressure is slowly applied.
• the load at the time of breakage of the spherical carrier is measured and the numerical values of 20 tests are arithmetically averaged.
• the so obtained catalysts contained To 100 Of a hydfosol Of baslc m m lfate the active metals of molybdenum and cobalt in the amounts 2 3, 1022 100 3 3 2 3 of 9.8-l0.1% by weight and 2.9-3.l% by weight, re- (11101ar P Was flddfid as the aterspectively insoluble inorganic solid material a hydrogel of aluminum
• y addlng a'mmonia 1 was impregnated with equal amounts of these metals by Water to elumltlum sulfate Solution, neutfflllzlng and the same procedure, followed by drying and calcining for water'washmg) 1n the amounts re'spgctlvely of 19D, 3 hours at 300 C. to prepare a catalyst, which w used 73.0, 170 and 255 grams, after whlch the several mixtures in Control 3.
• the catalysts were presulfided after their pack- 3 g g g fi zg s gg g a 2 g at f i ing but before their use, using a gas mixture of hydrogen 6 p g r Pwlse mm 8 Op d h d Ifid Th of the column whlle malntammg the temperature of the an y rogen 2 C e reaclon f a solvent at 85-90 C.
• the starting dispersion mixture tenfpelature of a Pressure 0 while being heated descended through the granulation a 1 1qu1d hourly SPaCe Veloclty of 1 vol/voL/Pf and a column to become a spherical hydrogel of 2-4 mm. diamffitlo of flow of hydrogen tofeedst'ock 011 of 9 eter. The hydrogel was immediately withdrawn from the liter-NTP/hter.
• the active metal content of the catalysts obtained in this manner were: molybdenum 9.8-10.12% by weight, cobalt 2.93.l% by weight and nickel 1.4-1.5 by weight.
• the hydrodesulfurization of an atmospheric distillation residuum of Khurusanya crude was carried out employing a fixed bed packed with the aforesaid catalysts.
• the presulfiding of the catalysts was not performed in any of the cases, and the reaction conditions used were: temperature 395 C., pressure kg./cm. g., liquid hourly space velocity of the feedstock oil 1 vol./vol./hr., ratio of rate of flow of hydrogen to feedstock oil 1100 liter-NTP/ liter.
• the desulfured oil leaving the reaction column was subjected to steam stripping to distill ofi hydrogen sulfide as well as other gases and cracked light oils, thus obtaining the product.
• Table 7. The changes that occurred in the total sulfur content of the products from the start of the test to 1000 hours are shown in Table 7. Further, the properties of the products at a point 500 hours after the start of the test are shown in Table 8.
• the desulfurization activity of the catalyst prepared in accordance with the present invention possesses a rate of maintenance that is exceedingly high.
• a catalyst composition for use in the catalytic hydrogenation of distillation residuum-containing petroleum hydrocarbons said catalyst composition being obtained by (a) passing a dispersion mixture through a waterimmiscible inert liquid medium to form a spherical gelled product, said dispersion mixture being composed of a sol selected from the group consisting of a hydrosol of basic aluminum sulfate and a hydrosol mixture of said hydrosol and a hydrosol of silica, said dispersion mixture having dispersed therein 565% by weight, based on the carrier to be obtained, of particles selected from the group consisting of a water-insoluble inorganic solid selected from the group consisting of aluminum hydroxide, activated alumina, alumina oxide, alumina hydrogel, silica gel, silica hydrogel, quartz, silica-alumina gel, silica-alumina hydrogel, aluminosilicates, metal oxides, metal hydroxides, and metal sulfides wherein the metal of

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (11)

• 1969
  • 1969-06-03 JP JP44042906A patent/JPS4931878B1/ja active Pending
• 1970
  • 1970-06-01 US US42463A patent/US3705861A/en not_active Expired - Lifetime
  • 1970-06-02 GB GB26675/70A patent/GB1285863A/en not_active Expired
  • 1970-06-03 DE DE2027329A patent/DE2027329C3/de not_active Expired

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